Energy transfer in non-covalent porphyrin assemblies: through-space or through-bond?

Photosynthetic antenna arrays found in nature funnel photoexcited energy into the reaction center. Attempts have been made to mimic the antenna function by using artificial chromophores, porphyrins in particular, not only to better understand the energy-transfer processes but also to create light-harvesting devices. This review covers non-covalent porphyrin assemblies, for which intra-ensemble energy-transfer processes were characterized. The essence of the mechanisms of energy transfer is summarized and specific examples are reviewed with an emphasis put on the rate and mechanism of singlet-singlet energy transfer. As these examples demonstrate, non-covalent intra-ensemble energy-transfer processes have been ascribed to the Forster-type through-space mechanism in almost all cases. The exception is porphyrin dyad and pentad from our group based on amidinium-carboxylate salt bridges. Through-bond superexchange mechanism is proposed to account for the fast excited energy-transfer processes for these unique assemblies. The importance of intermolecular interactions not only in terms of the structural aspects but also in terms of the electronic aspects is highlighted for the design of supramolecular systems in which efficient energy transfer is desired.